US20190381486A1 - Manganese-doped nickel-methanation catalysts - Google Patents
Manganese-doped nickel-methanation catalysts Download PDFInfo
- Publication number
- US20190381486A1 US20190381486A1 US16/479,283 US201816479283A US2019381486A1 US 20190381486 A1 US20190381486 A1 US 20190381486A1 US 201816479283 A US201816479283 A US 201816479283A US 2019381486 A1 US2019381486 A1 US 2019381486A1
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- United States
- Prior art keywords
- catalyst
- precipitate
- methanation
- solution
- manganese
- Prior art date
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 239000002244 precipitate Substances 0.000 claims abstract description 23
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000975 co-precipitation Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000002955 isolation Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 150000008040 ionic compounds Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 55
- 239000011572 manganese Substances 0.000 description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- -1 carboxyl ions Chemical class 0.000 description 5
- 238000011067 equilibration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- 239000003637 basic solution Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910017107 AlOx Inorganic materials 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- LFYMLMKKOJHYFY-UHFFFAOYSA-N [O-2].[Al+3].[Ni+2] Chemical compound [O-2].[Al+3].[Ni+2] LFYMLMKKOJHYFY-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012482 calibration solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
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- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
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- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/889—Manganese, technetium or rhenium
Definitions
- Methane can be easily stored in existing infrastructure, which has storage capacity for periods of months, can be transported long distances with almost zero losses, and can be converted back to power as and when required.
- the methanation reaction which is associated with high energy release and is usually catalyzed, is the cornerstone of the process.
- the high exothermicity of the reaction ( ⁇ 165 kJ/mol) gives rise to two direct problems. Firstly, at high temperatures, the thermodynamic equilibrium places limits on the maximum methane yield that can be achieved. For methane to be fed into the natural gas grid in Germany, a purity of 95% is necessary. This necessitates catalysts with high activity that allow higher methane yields to be achieved at the reaction pressures and low temperatures employed in industry.
- the methanation reaction uses mainly nickel-based catalysts, but there are also approaches using other active metals, for example ruthenium or rhodium.
- As the support in addition to aluminum oxide, oxides of silicon, titanium, and zirconium are also used. Descriptions of such systems are given, for example, in published patent applications CN 104043454 A, CN 103480375 A, CN 102091629 A, CN 104888783 A, and WO 2008110331 A1.
- catalysts that not only contain an active metal, but include promoters. As disclosed in the literature, promotion with iron or manganese can have a beneficial effect on catalyst performance.
- Doping with manganese is described, for example, in CN 103464163 A, CN 103752315 A, CN 102600860 A, CN 102553610 A, CN 102527405 A, CN 102513124 A, CN 102463120 A, CN 102463119 A, CN 103706366 A, CN 104028270 A, and CN 101745401 A and by Zhao et al., Journal of Natural Gas Chemistry (2012), 21(2), 170-177 and Gao et al. Journal of molecular catalysis (China), vol. 25, No. 1, February 2011.
- CN 103752315 A relates to a catalyst present on a metallic support phase and also the method of preparation and use of the catalyst in the production of methane and synthetic methane gas production through the catalytic conversion of carbon monoxide and/or carbon dioxide.
- the catalyst present on the metallic support phase comprises as active component a metal oxide present on the metallic support phase and an auxiliary metal oxide; the formula of the catalyst present on the metallic support phase is xM1O-yM2O/ZT, where M1O is the metal oxide as active component, ZT the metallic support phase, x the percentage by weight of the metal oxide as active component in the catalyst, and y is the percentage by weight of the auxiliary metal oxide.
- CN 102600860 A relates to a catalyst that is suitable for the complete methanation of synthesis gas at moderate or lower temperatures.
- the catalyst comprises the following components in percent by weight: 12 to 26% nickel, 1 to 4% manganese, 0.1 to 2% of one or more of lanthanum, calcium and/or magnesium, the balance being a composite support containing aluminum oxide and cerium oxide, wherein the sum of the percentages by weight of the components is 100% and the cerium oxide content of the composite support is 6 to 12%.
- the catalyst is prepared by the steps: (1) formation of the composite support; (2) preparation of the impregnation solution; (3) treatment by a modified pressure impregnation method; and (4) heating the impregnated catalyst to 500 to 600° C. and calcining for 6 to 8 hours to obtain the desired product.
- CN 102527405 A discloses a catalyst used for the complete methanation of synthesis gas at high temperature, wherein the catalyst comprises the following constituents in percent by weight: 10 to 30% by weight nickel, 11 to 20% by weight lanthanum, 1 to 5% by weight cerium, 0.1 to 2% by weight of one or more of manganese, lithium, and vanadium, with the balance comprising aluminum oxide, the sum of the percentages by weight of these constituents being 100%.
- the method of preparation of the catalyst comprises the following steps: (1) combination and mixing of the catalyst constituents; (2) drying to obtain a mixture; (3) heating the mixture to 600 to 800° C. at a heating rate of 1 to 4° C. per minute and calcining at a temperature between 600 and 800° C. for 6 to 8 hours to obtain a product in powder form; and (4) milling the product powder and treatment by a pressure impregnation method to obtain the target product.
- CN 102513124 A discloses a technology for the production of synthetic natural gas by methanation of carbon oxides and provides a catalyst for the methanation of coke oven gas and a method of preparation thereof.
- the catalyst is a ⁇ -alumina or a titanium dioxide support to stabilize the active component and an additive, wherein the active component is Ni and the additive consists of a first additive and a second additive; the first additive is a rare earth element and the second additive one or a combination of two or more of Sr, Mn, V, Zr, Ce, and Cr.
- CN 102463120 A discloses a catalyst containing nickel and manganese and its preparation and use.
- the catalyst containing nickel and manganese contains a) nickel oxide, wherein the nickel content is in the range from 15 to 55% by weight and b) manganese oxide, wherein the manganese content is in the range from 0.1 to 15% by weight.
- At least one of alumina, silica, titanium dioxide, and zirconium dioxide is used as catalyst support.
- the method of preparation comprises steps of dissolving a nickel salt and a manganese salt in an organic acid solution, wetting the catalyst support with the mixed solution obtained in the previous step, drying in a thermolysis to obtain the nickel- and manganese-containing catalyst.
- the organic acid solution is an organic carboxylic acid or a reducing organic acid, wherein the molar ratio of the overall charge of the carboxyl ions of the organic acid to the metal ions is between 0.5 to 3:1 and the molar ratio of the reducing organic acid to the metal ions is 0.2 to 2:1.
- CN 102463119 A discloses a methanation catalyst and its preparation.
- the methanation catalyst comprises the following components: a) nickel oxide, wherein the nickel content is between 5 and 50% by weight; b) manganese oxide, wherein the manganese content is from 0.1 to 15% by weight; c) at least one of the oxides of beryllium, manganese, calcium, strontium, barium, lanthanum, and cerium, wherein the metal content is between 0.5 and 20% by weight, with component c) distributed throughout the support particles.
- the disclosed preparation comprises the following steps: 1) combined dissolution of a nickel salt and/or a manganese salt in an organic acid, preparation of a salt of component c) in an aqueous solution; and 2) wetting the components to be stabilized, the nickel, the manganese, and component c), wherein component c) is stabilized independently, and calcining and a sintering/disintegration treatment is carried out after each stabilization.
- CN 103706366 A discloses a catalyst comprising 15 to 55% of an active component, 1 to 6% of a first catalytic promoter, 3 to 15% of a second catalytic promoter, the balance being a catalyst support, wherein the active component is nickel oxide, the catalytic support is Al 2 O 3 , the first catalytic promoter is one selected from lanthanum oxide, cerium oxide or samarium oxide, and the second catalytic promoter is at least one from magnesium oxide, manganese oxide, iron oxide, and zirconium oxide.
- the method of preparation comprises the steps: dissolution of a reductant in water to obtain a reducing solution, mixing nickel nitrate, aluminum nitrate, the first metal salt, and the second metal salt into water to obtain a raw material solution, and addition of the reducing mixture to the starting material solution with steady stirring to obtain a first solution, transfer to a sealed reactor and performance of a reaction at 100 to 200° C. for 10 to 15 hours, cooling to room temperature, filtering and washing to a pH of 6 to 7, drying at 80 to 120° C. for 4 to 30 hours, and calcining at 300 to 550° C.
- the reductant is one selected from formaldehyde, hydrazine hydrate, sodium hypophosphite, and ascorbic acid
- the first metal salt is one selected from lanthanum nitrate, cerium nitrate, and samarium nitrate
- the second metal salt is at least one selected from magnesium nitrate, manganese nitrate, iron nitrate, and zirconium nitrate
- the alkali solution is an aqueous solution of sodium carbonate, sodium hydroxide, potassium carbonate, ammonium carbonate, urea or NH 3 .H 2 O.
- the catalyst may be mixed with a binder (calcium aluminate), a lubricant (graphite), and water and then pressed into particle form.
- the catalyst is suitable for the methanation of coal gas at high temperature and high pressure in order to produce synthetic natural gas.
- CN 104028270 A discloses a methanation catalyst comprising 5 to 60% by weight of a catalytically active NiO component, based on the total weight of catalyst, the balance comprising Al 2 O 3 , which can likewise contain 1 to 25% by weight, based on the total weight of catalyst, of a co-catalyst component M, wherein the co-catalyst component M is selected from one or more oxides of the metals Ce, Ca, Co, La, Sm, Zr, Ba, Mn, Fe, Mo, Ti and Cu.
- the document also provides a method for preparing the methanation catalyst; this comprises mixing of the precursor for the catalytically active component, of the precursor for the co-catalyst component M, and of a catalyst support according to the corresponding proportion in the methanation catalyst composition, addition of an organic fuel, thorough mixing and drying to form a gel-like product, performance of a combustion reaction, cleaning, and drying to obtain the final product.
- CN 101745401 A discloses a supported, sulfur-resistant methanation catalyst which features a main metal M as active component, a second metal M1 as adjuvant, and S as support material, wherein the weight ratio between M1, M, and S is 0.01 to 39:1 to 30:0.01 to 90, M is Mo, W, and/or V, the second metal M1 is one or more of Fe, Co, Ni, Cr, Mn, La, Y, or/and Ce, and the support S is ZrO 2 , Al 2 O 3 , MgO or TiO 2 .
- the supported, sulfur-resistant methanation catalyst is prepared by a sol-gel method.
- a catalyst for the methanation of carbon monoxide and/or carbon dioxide comprising aluminum oxide, a Ni active mass, and Mn, wherein the Ni/Mn molar ratio in the catalyst is 3.0 to 10.0, preferably 4.0 to 9.0, and more preferably 5.5 to 6.5.
- the Ni/Mn ratio can also be in the range from 6.0 to 10.0, preferably in the range from 7.0 to 9.0, and most preferably in the range from 7.5 to 8.5.
- the aluminum oxide does not need to be stoichiometric Al 2 O 3 , but can instead also be non-stoichiometric aluminum oxide.
- the promoter Mn may be present wholly or partly in the Ni active mass.
- the catalyst may contain further promoters besides Mn, but likewise may contain exclusively Mn as promoter.
- the oxidation states of Al, Ni, and the promoters may vary according to how the catalyst is treated.
- Al, Ni, and the promoters are typically present as metal cations (e.g. Al 3+ , Ni 2+ , Mn 2+ , Mn 3+ , Mn 4+ ). After calcination, for example in air, high oxidation states or the maximum oxidation states may be reached. If the catalyst is reduced at temperatures above room temperature, for example under reaction conditions with hydrogen, Al, Ni, and the promoters may adopt lower oxidation states or be partly or completely present in oxidation state 0.
- the charge of the metal cations is counterbalanced by oxygen anions (O 2 ⁇ ).
- the catalyst according to the invention may contain further components besides aluminum oxide (AlO x , where x ⁇ 1.5), Ni, and Mn (and the oxygen anions needed to counterbalance the charge), but it may also consist exclusively of aluminum oxide, Ni, and Mn.
- the Ni active mass may likewise contain further promoters besides Mn, including for example Fe, but it may also contain exclusively the promoter Mn.
- the Ni active mass preferably contains none of the elements Ta, In, Cu, Ce, Cr, Bi, Fe, P, Sb, Sn, B, Si, Ti, Zr, Co, Rh, Ru, Ag, Ir, Pd, and Pt.
- the Ni active mass preferably does not contain any noble metal.
- the Al/Ni atomic ratio may be between 0.5 and 1.5, preferably between 0.8 and 1.2; the Al/Ni ratio is more preferably approximately 1.
- the catalyst according to the invention may advantageously contain, in the Ni active mass, crystallites with a diameter below 20 mm, preferably below 10 mm.
- the Ni active mass may even consist entirely or in substantial parts of crystallites with a diameter below 20 mm, preferably below 10 mm.
- the Ni active mass is preferably in a metallic state.
- the CO 2 uptake capacity of the catalysts at 35° C. may be greater than 150 ⁇ mol/g and is preferably in the range from 150 to 350 ⁇ mol/g, more preferably from 180 to 260 ⁇ mol/g.
- the BET surface area (S BET ) of the catalyst according to the invention may be greater than 100 m 2 /g, preferably greater than 200 m 2 /g, or in the range from 200 to 400 m 2 /g, preferably in the range from 200 to 300 m 2 /g, and especially preferably in the range from 200 to 250 m 2 /g.
- the specific metal surface area (S met ) of the catalyst according to the invention is preferably greater than 5 m 2 /g, preferably greater than 10 m 2 /g or in the range from 10 to 30 m 2 /g, preferably in the range from 15 to 25 m 2 /g or in the range from 17 to 23 m 2 /g.
- the invention also relates to a method for the preparation of a methanation catalyst comprising the steps:
- the solution from step a) here is preferably an aqueous solution and Al, Ni, and Mn are present in the aqueous solution as dissolved ionic compounds.
- Al is dissolved preferably as aluminum nitrate, aluminum trichloride or aluminum sulfate.
- Ni is dissolved preferably as nickel nitrate, nickel dichloride, nickel sulfate, nickel acetate or nickel carbonate.
- Mn is preferably present in oxidation state II or IV and dissolved as manganese nitrate, manganese acetate, manganese dichloride, manganese sulfate or else in oxidation state VII as permanganate ion.
- Co-precipitation is carried out by addition of the solution containing Al, Ni, and Mn to an initial change of a basic solution or by addition of a basic solution to the initially charged solution containing Al, Ni, and Mn.
- the solution containing Al, Ni, and Mn and the basic solution are simultaneously added to a vessel already containing a solvent such as water and mixed therein.
- the basic solution has a pH greater than 7, preferably in the range from 8 to 10, and preferably contains an alkali metal hydroxide and/or an alkali metal carbonate, for example a mixture of sodium hydroxide and sodium carbonate.
- the co-precipitation is carried out preferably with temperature regulation so that the temperature of the solution is close to room temperature or, for example, 30° C.
- Al, Ni, and Mn are preferably in dissolved form, present in the aqueous solution as ionic compounds, and have the same anion, which may for example be nitrate.
- the precipitate is preferably aged in the solution for at least 30 minutes, preferably for longer than 1 hour, and more preferably for longer than 12 hours.
- the ageing is preferably carried out by stirring the precipitate in the solution (mother liquor) at approximately room temperature.
- the precipitate obtained by co-precipitation is isolated, for example by conducting a filtration.
- the filtration may suitably be carried out using, for example, a filter press.
- the isolated precipitate is preferably washed to neutral pH, for example with distilled water.
- the isolated precipitate may subsequently be dried, for example at elevated temperature in air. Drying is preferably carried out at a temperature between 70° C. and 90° C. for a period longer than 4 hours, preferably longer than 12 hours.
- the isolated precipitate is calcined; this can be carried out in air at a temperature between 300° C. and 600° C., preferably at 400° C. to 500° C., and for a period of 3 hours to 10 hours, preferably 5 to 7 hours.
- the catalyst according to the invention is to be used especially in the methanation of carbon monoxide and/or carbon dioxide.
- the methanation of carbon dioxide can be represented by the following reaction equation:
- the methanation of carbon monoxide can be represented by the following reaction equation:
- the reaction gas which contains carbon dioxide and/or carbon monoxide or a mixture of the two is brought into contact with the catalyst at a temperature above 200° C.
- FIGS. 1 to 4 show the catalytic profile of the manganese-doped catalysts Mn1, Mn4, Mn6, and Mn8 before and after ageing.
- FIG. 1 Catalytie test results for Mn1 (comparative example)
- FIG. 2 Catalytie test results for Mn4 (example)
- FIG. 3 Catalytie test results for Mn6 (example)
- FIG. 4 Catalytie test results for Mn8 (comparative example)
- FIG. 5 Activity/stability diagram for the described samples.
- the composition of the calcined catalysts was determined by inductively-coupled plasma optical emission spectroscopy (ICP-OES). 50 mg of catalyst was dissolved in 50 ml of 1 molar phosphoric acid (VWR, analytical grade) at 60° C. To dissolve the manganese dioxide that forms, 50 mg of Na 2 SO 3 (Sigma-Aldrich, analytical grade) was added to the solution. The solutions were cooled and then diluted 1/10 and filtered through 0.1 ⁇ m filters (Pall). The calibration solutions were made up at concentrations of 1, 10, and 50 mg l ⁇ 1 (Merck). The metal concentrations were determined using an Agilent 700 ICP-OES.
- the specific surface areas of the catalysts were determined by N 2 -BET analysis on a Nova 4000e (Quantachrome). For this, 100 mg of catalyst was degassed for 3 hours at 120° C. and adsorption and desorption isotherms were then recorded in the 0.007 to 1 p/p 0 range. The BET surface area was determined using the data points in the 0.007 to 0.28 p/p 0 range.
- Chemisorption experiments were carried out on an Autosorb 1C (Quantachrome). Before measurement, 100 mg of catalyst was activated at 500° C. in 10% H 2 in N 2 for 6 hours. The heating ramp was 2 K min ⁇ 1 .
- the metal surface area (S MET ) was determined in accordance with DIN 66136-2 (vers. 2007-01) by H 2 chemisorption at 35° C. For this purpose, 20 adsorption points were recorded equidistantly from 40 mmHg to 800 mmHg. The equilibration time was 2 min for adsorption and 10 min for thermal equilibration. For the determination of the metal surface area, the metal atom/H stoichiometry was set at 1. For the CO 2 chemisorption measurements to determine the CO 2 uptake capacity (U(CO 2 )), the equilibration time for adsorption was set at 10 min with the parameters otherwise unchanged. Before recording the chemisorption data, any kinetic inhibition of CO 2 chemisorption under these conditions was ruled out experimentally. Metal surface areas and CO 2 uptake capacities were extrapolated to a pressure of 0 mmHg by the extrapolation method.
- the catalysts were prepared by co-precipitation, with the nickel/aluminum atomic ratio set at 1.
- iron(III) nitrate was added to the nickel nitrate/aluminum nitrate salt solution during the synthesis of the catalyst.
- manganese(II) nitrate and iron(III) nitrate were added to the nickel nitrate/aluminum nitrate salt solution during the synthesis of the catalyst. All chemicals used were of analytical grade purity. Water was purified in a Millipore filter system and the purity verified by conductivity measurements.
- the synthesis was carried out in a double-jacketed stirred-tank reactor with a capacity of 3 I.
- the thermostat fitted to the water-filled double jacket allowed the temperature to be maintained at 30° C. during the synthesis run and two baffles were employed for better mixing.
- Stirring was carried out using a precision glass stirrer operating at 150 rpm.
- the stirred-tank reactor was charged with 1 I of H 2 O, which was adjusted to pH 9 ⁇ 0.1.
- the addition of the mixture of dissolved nitrates was carried out at a rate of 2.5 ml min ⁇ 1 .
- the controlled addition of the precipitation reagent at the same time served to maintain the pH.
- the starting materials used were one-molar solutions of the respective nitrates (Ni(NO 3 ) 2 .6H 2 O, Al(NO 3 ) 2 .9H 2 O, Fe(NO 3 ) 3 .9H 2 O, and Mn(NO 3 ) 2 .4H 2 O). These were mixed, as shown in Table 2, to a total volume of 120 ml min ⁇ 1 before undergoing dropwise addition to the reactor.
- the precipitation reagent used was a mixture of equal volumes of 0.5 M NaOH and 0.5 M Na 2 CO 3 solutions, which was added using a titrator.
- the suspension was aged overnight in the mother liquor with constant stirring, after which the precipitate was filtered off and washed with H 2 O until the filtrate was of neutral pH. After drying overnight at 80° C. in a drying cabinet, the dried precipitate (precursor) was heated to 450° C. at a heating rate of 5 K min ⁇ 1 and calcined for 6 hours in synthetic air.
- the temperature T75.1 necessary to achieve a CO 2 conversion of 75% during the S-curve 1 measurement step was determined.
- the temperature was increased in 25° C. increments in the specified range. The lower T75.1 is, the higher therefore the activity of the catalyst.
- the temperature T75.2 necessary to achieve a CO 2 conversion of 75% during the S-curve 2 measurement step was determined.
- the temperature was increased in 25° C. increments in the specified range. The lower T75.2 is, the higher therefore the activity of the catalyst after ageing.
- Normalized ⁇ ⁇ activity T 75.1 ⁇ ( Ni ⁇ / ⁇ AlO x ) T 75.1 ⁇ ( dop . cat . )
- Normalized ⁇ ⁇ stability T 75.2 ⁇ ( Ni ⁇ / ⁇ AlO x ) T 75.1 ⁇ ( Ni ⁇ / ⁇ AlO x ) T 75.2 ⁇ ( dop . cat . ) T 75.1 ⁇ ( dop . cat . )
- FIGS. 1 to 4 show that addition of a manganese promoter to a Ni/AlO x catalyst results in a significant increase in catalyst activity.
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Abstract
Description
- The supply of energy through the so-called renewable energies of photovoltaics and wind energy suffers from the problem of fluctuations in power production due to weather and time of day. To ensure security of supply, a way must be found that absorbs fluctuations in power production due to weather and time of day. One potential method of storing energy chemically is the power-to-gas process, in which surplus power is used to cleave water electrolytically into hydrogen and oxygen. Hydrogen, in which the energy obtained by electrolysis of water is stored, can itself be stored or transported to the end user only at high expense. In the power-to-gas process, the hydrogen therefore undergoes a methanation reaction to methane and water in a further reaction step with carbon dioxide, which in the atmosphere acts as a climate-damaging greenhouse gas. Methane can be easily stored in existing infrastructure, which has storage capacity for periods of months, can be transported long distances with almost zero losses, and can be converted back to power as and when required. The methanation reaction, which is associated with high energy release and is usually catalyzed, is the cornerstone of the process. The high exothermicity of the reaction (−165 kJ/mol) gives rise to two direct problems. Firstly, at high temperatures, the thermodynamic equilibrium places limits on the maximum methane yield that can be achieved. For methane to be fed into the natural gas grid in Germany, a purity of 95% is necessary. This necessitates catalysts with high activity that allow higher methane yields to be achieved at the reaction pressures and low temperatures employed in industry.
- When reactors are operated adiabatically, the high exothermicity of the methanation reaction can sometimes cause hotspots to develop in the reactor. This can result in high local temperatures being reached that can damage the catalyst. To minimize the cost of catalyst replacement/shutdown times and material costs, there is accordingly high interest in developing catalyst systems that are as stable as possible. The need also arises for catalysts for the CO2 methanation reaction that are as active and selective as possible.
- The methanation reaction uses mainly nickel-based catalysts, but there are also approaches using other active metals, for example ruthenium or rhodium. As the support, in addition to aluminum oxide, oxides of silicon, titanium, and zirconium are also used. Descriptions of such systems are given, for example, in published patent applications CN 104043454 A, CN 103480375 A, CN 102091629 A, CN 104888783 A, and WO 2008110331 A1.
- There are additionally catalysts that not only contain an active metal, but include promoters. As disclosed in the literature, promotion with iron or manganese can have a beneficial effect on catalyst performance.
- Doping with manganese is described, for example, in CN 103464163 A, CN 103752315 A, CN 102600860 A, CN 102553610 A, CN 102527405 A, CN 102513124 A, CN 102463120 A, CN 102463119 A, CN 103706366 A, CN 104028270 A, and CN 101745401 A and by Zhao et al., Journal of Natural Gas Chemistry (2012), 21(2), 170-177 and Gao et al. Journal of molecular catalysis (China), vol. 25, No. 1, February 2011.
- CN 103752315 A relates to a catalyst present on a metallic support phase and also the method of preparation and use of the catalyst in the production of methane and synthetic methane gas production through the catalytic conversion of carbon monoxide and/or carbon dioxide. The catalyst present on the metallic support phase comprises as active component a metal oxide present on the metallic support phase and an auxiliary metal oxide; the formula of the catalyst present on the metallic support phase is xM1O-yM2O/ZT, where M1O is the metal oxide as active component, ZT the metallic support phase, x the percentage by weight of the metal oxide as active component in the catalyst, and y is the percentage by weight of the auxiliary metal oxide.
- CN 102600860 A relates to a catalyst that is suitable for the complete methanation of synthesis gas at moderate or lower temperatures. The catalyst comprises the following components in percent by weight: 12 to 26% nickel, 1 to 4% manganese, 0.1 to 2% of one or more of lanthanum, calcium and/or magnesium, the balance being a composite support containing aluminum oxide and cerium oxide, wherein the sum of the percentages by weight of the components is 100% and the cerium oxide content of the composite support is 6 to 12%. The catalyst is prepared by the steps: (1) formation of the composite support; (2) preparation of the impregnation solution; (3) treatment by a modified pressure impregnation method; and (4) heating the impregnated catalyst to 500 to 600° C. and calcining for 6 to 8 hours to obtain the desired product.
- CN 102527405 A discloses a catalyst used for the complete methanation of synthesis gas at high temperature, wherein the catalyst comprises the following constituents in percent by weight: 10 to 30% by weight nickel, 11 to 20% by weight lanthanum, 1 to 5% by weight cerium, 0.1 to 2% by weight of one or more of manganese, lithium, and vanadium, with the balance comprising aluminum oxide, the sum of the percentages by weight of these constituents being 100%. The method of preparation of the catalyst comprises the following steps: (1) combination and mixing of the catalyst constituents; (2) drying to obtain a mixture; (3) heating the mixture to 600 to 800° C. at a heating rate of 1 to 4° C. per minute and calcining at a temperature between 600 and 800° C. for 6 to 8 hours to obtain a product in powder form; and (4) milling the product powder and treatment by a pressure impregnation method to obtain the target product.
- CN 102513124 A discloses a technology for the production of synthetic natural gas by methanation of carbon oxides and provides a catalyst for the methanation of coke oven gas and a method of preparation thereof. The catalyst is a γ-alumina or a titanium dioxide support to stabilize the active component and an additive, wherein the active component is Ni and the additive consists of a first additive and a second additive; the first additive is a rare earth element and the second additive one or a combination of two or more of Sr, Mn, V, Zr, Ce, and Cr.
- CN 102463120 A discloses a catalyst containing nickel and manganese and its preparation and use. The catalyst containing nickel and manganese contains a) nickel oxide, wherein the nickel content is in the range from 15 to 55% by weight and b) manganese oxide, wherein the manganese content is in the range from 0.1 to 15% by weight. At least one of alumina, silica, titanium dioxide, and zirconium dioxide is used as catalyst support. The method of preparation comprises steps of dissolving a nickel salt and a manganese salt in an organic acid solution, wetting the catalyst support with the mixed solution obtained in the previous step, drying in a thermolysis to obtain the nickel- and manganese-containing catalyst. The organic acid solution is an organic carboxylic acid or a reducing organic acid, wherein the molar ratio of the overall charge of the carboxyl ions of the organic acid to the metal ions is between 0.5 to 3:1 and the molar ratio of the reducing organic acid to the metal ions is 0.2 to 2:1.
- CN 102463119 A discloses a methanation catalyst and its preparation. The methanation catalyst comprises the following components: a) nickel oxide, wherein the nickel content is between 5 and 50% by weight; b) manganese oxide, wherein the manganese content is from 0.1 to 15% by weight; c) at least one of the oxides of beryllium, manganese, calcium, strontium, barium, lanthanum, and cerium, wherein the metal content is between 0.5 and 20% by weight, with component c) distributed throughout the support particles. The disclosed preparation comprises the following steps: 1) combined dissolution of a nickel salt and/or a manganese salt in an organic acid, preparation of a salt of component c) in an aqueous solution; and 2) wetting the components to be stabilized, the nickel, the manganese, and component c), wherein component c) is stabilized independently, and calcining and a sintering/disintegration treatment is carried out after each stabilization.
- CN 103706366 A discloses a catalyst comprising 15 to 55% of an active component, 1 to 6% of a first catalytic promoter, 3 to 15% of a second catalytic promoter, the balance being a catalyst support, wherein the active component is nickel oxide, the catalytic support is Al2O3, the first catalytic promoter is one selected from lanthanum oxide, cerium oxide or samarium oxide, and the second catalytic promoter is at least one from magnesium oxide, manganese oxide, iron oxide, and zirconium oxide. The method of preparation comprises the steps: dissolution of a reductant in water to obtain a reducing solution, mixing nickel nitrate, aluminum nitrate, the first metal salt, and the second metal salt into water to obtain a raw material solution, and addition of the reducing mixture to the starting material solution with steady stirring to obtain a first solution, transfer to a sealed reactor and performance of a reaction at 100 to 200° C. for 10 to 15 hours, cooling to room temperature, filtering and washing to a pH of 6 to 7, drying at 80 to 120° C. for 4 to 30 hours, and calcining at 300 to 550° C. for 2 to 12 hours to obtain a catalyst, wherein the reductant is one selected from formaldehyde, hydrazine hydrate, sodium hypophosphite, and ascorbic acid, where the first metal salt is one selected from lanthanum nitrate, cerium nitrate, and samarium nitrate, the second metal salt is at least one selected from magnesium nitrate, manganese nitrate, iron nitrate, and zirconium nitrate, and the alkali solution is an aqueous solution of sodium carbonate, sodium hydroxide, potassium carbonate, ammonium carbonate, urea or NH3.H2O. The catalyst may be mixed with a binder (calcium aluminate), a lubricant (graphite), and water and then pressed into particle form. The catalyst is suitable for the methanation of coal gas at high temperature and high pressure in order to produce synthetic natural gas.
- CN 104028270 A discloses a methanation catalyst comprising 5 to 60% by weight of a catalytically active NiO component, based on the total weight of catalyst, the balance comprising Al2O3, which can likewise contain 1 to 25% by weight, based on the total weight of catalyst, of a co-catalyst component M, wherein the co-catalyst component M is selected from one or more oxides of the metals Ce, Ca, Co, La, Sm, Zr, Ba, Mn, Fe, Mo, Ti and Cu. The document also provides a method for preparing the methanation catalyst; this comprises mixing of the precursor for the catalytically active component, of the precursor for the co-catalyst component M, and of a catalyst support according to the corresponding proportion in the methanation catalyst composition, addition of an organic fuel, thorough mixing and drying to form a gel-like product, performance of a combustion reaction, cleaning, and drying to obtain the final product.
- CN 101745401 A discloses a supported, sulfur-resistant methanation catalyst which features a main metal M as active component, a second metal M1 as adjuvant, and S as support material, wherein the weight ratio between M1, M, and S is 0.01 to 39:1 to 30:0.01 to 90, M is Mo, W, and/or V, the second metal M1 is one or more of Fe, Co, Ni, Cr, Mn, La, Y, or/and Ce, and the support S is ZrO2, Al2O3, MgO or TiO2. The supported, sulfur-resistant methanation catalyst is prepared by a sol-gel method.
- It is an object of the invention to provide a methanation catalyst for the methanation of carbon monoxide and/or carbon dioxide that, alongside high selectivity and stability, shows improved activity compared with catalysts of the prior art.
- This object is achieved by a catalyst for the methanation of carbon monoxide and/or carbon dioxide comprising aluminum oxide, a Ni active mass, and Mn, wherein the Ni/Mn molar ratio in the catalyst is 3.0 to 10.0, preferably 4.0 to 9.0, and more preferably 5.5 to 6.5.
- The Ni/Mn ratio can also be in the range from 6.0 to 10.0, preferably in the range from 7.0 to 9.0, and most preferably in the range from 7.5 to 8.5.
- The aluminum oxide does not need to be stoichiometric Al2O3, but can instead also be non-stoichiometric aluminum oxide.
- The promoter Mn may be present wholly or partly in the Ni active mass. The catalyst may contain further promoters besides Mn, but likewise may contain exclusively Mn as promoter. The oxidation states of Al, Ni, and the promoters may vary according to how the catalyst is treated. Al, Ni, and the promoters are typically present as metal cations (e.g. Al3+, Ni2+, Mn2+, Mn3+, Mn4+). After calcination, for example in air, high oxidation states or the maximum oxidation states may be reached. If the catalyst is reduced at temperatures above room temperature, for example under reaction conditions with hydrogen, Al, Ni, and the promoters may adopt lower oxidation states or be partly or completely present in
oxidation state 0. The charge of the metal cations is counterbalanced by oxygen anions (O2−). - The catalyst according to the invention may contain further components besides aluminum oxide (AlOx, where x≤1.5), Ni, and Mn (and the oxygen anions needed to counterbalance the charge), but it may also consist exclusively of aluminum oxide, Ni, and Mn. The Ni active mass may likewise contain further promoters besides Mn, including for example Fe, but it may also contain exclusively the promoter Mn. The Ni active mass preferably contains none of the elements Ta, In, Cu, Ce, Cr, Bi, Fe, P, Sb, Sn, B, Si, Ti, Zr, Co, Rh, Ru, Ag, Ir, Pd, and Pt. The Ni active mass preferably does not contain any noble metal.
- The Al/Ni atomic ratio may be between 0.5 and 1.5, preferably between 0.8 and 1.2; the Al/Ni ratio is more preferably approximately 1.
- The catalyst according to the invention may advantageously contain, in the Ni active mass, crystallites with a diameter below 20 mm, preferably below 10 mm. The Ni active mass may even consist entirely or in substantial parts of crystallites with a diameter below 20 mm, preferably below 10 mm. The Ni active mass is preferably in a metallic state.
- The CO2 uptake capacity of the catalysts at 35° C. may be greater than 150 μmol/g and is preferably in the range from 150 to 350 μmol/g, more preferably from 180 to 260 μmol/g.
- The BET surface area (SBET) of the catalyst according to the invention may be greater than 100 m2/g, preferably greater than 200 m2/g, or in the range from 200 to 400 m2/g, preferably in the range from 200 to 300 m2/g, and especially preferably in the range from 200 to 250 m2/g.
- The specific metal surface area (Smet) of the catalyst according to the invention is preferably greater than 5 m2/g, preferably greater than 10 m2/g or in the range from 10 to 30 m2/g, preferably in the range from 15 to 25 m2/g or in the range from 17 to 23 m2/g.
- The invention also relates to a method for the preparation of a methanation catalyst comprising the steps:
-
- a) co-precipitation from a solution containing Al, Ni, and Mn in dissolved form to obtain a precipitate,
- b) isolation of the precipitate from step a),
- c) drying of the isolated precipitate from step b), and
- d) calcining of the dried precipitate from step c).
- The solution from step a) here is preferably an aqueous solution and Al, Ni, and Mn are present in the aqueous solution as dissolved ionic compounds.
- Al is dissolved preferably as aluminum nitrate, aluminum trichloride or aluminum sulfate. Ni is dissolved preferably as nickel nitrate, nickel dichloride, nickel sulfate, nickel acetate or nickel carbonate. Mn is preferably present in oxidation state II or IV and dissolved as manganese nitrate, manganese acetate, manganese dichloride, manganese sulfate or else in oxidation state VII as permanganate ion.
- Co-precipitation is carried out by addition of the solution containing Al, Ni, and Mn to an initial change of a basic solution or by addition of a basic solution to the initially charged solution containing Al, Ni, and Mn. Alternatively, the solution containing Al, Ni, and Mn and the basic solution are simultaneously added to a vessel already containing a solvent such as water and mixed therein. The basic solution has a pH greater than 7, preferably in the range from 8 to 10, and preferably contains an alkali metal hydroxide and/or an alkali metal carbonate, for example a mixture of sodium hydroxide and sodium carbonate. The co-precipitation is carried out preferably with temperature regulation so that the temperature of the solution is close to room temperature or, for example, 30° C.
- Al, Ni, and Mn are preferably in dissolved form, present in the aqueous solution as ionic compounds, and have the same anion, which may for example be nitrate.
- After the precipitation (co-precipitation), the precipitate is preferably aged in the solution for at least 30 minutes, preferably for longer than 1 hour, and more preferably for longer than 12 hours. The ageing is preferably carried out by stirring the precipitate in the solution (mother liquor) at approximately room temperature.
- The precipitate obtained by co-precipitation is isolated, for example by conducting a filtration. The filtration may suitably be carried out using, for example, a filter press.
- The isolated precipitate is preferably washed to neutral pH, for example with distilled water.
- The isolated precipitate may subsequently be dried, for example at elevated temperature in air. Drying is preferably carried out at a temperature between 70° C. and 90° C. for a period longer than 4 hours, preferably longer than 12 hours.
- The isolated precipitate is calcined; this can be carried out in air at a temperature between 300° C. and 600° C., preferably at 400° C. to 500° C., and for a period of 3 hours to 10 hours, preferably 5 to 7 hours.
- The catalyst according to the invention is to be used especially in the methanation of carbon monoxide and/or carbon dioxide. The methanation of carbon dioxide can be represented by the following reaction equation:
-
4H2+CO2-->CH4+2H2O - The methanation of carbon monoxide can be represented by the following reaction equation:
-
3H2+CO-->CH4+H2O - In the process for performing the methanation, the reaction gas which contains carbon dioxide and/or carbon monoxide or a mixture of the two is brought into contact with the catalyst at a temperature above 200° C.
-
FIGS. 1 to 4 show the catalytic profile of the manganese-doped catalysts Mn1, Mn4, Mn6, and Mn8 before and after ageing. -
FIG. 1 : Catalytie test results for Mn1 (comparative example) -
FIG. 2 : Catalytie test results for Mn4 (example) -
FIG. 3 : Catalytie test results for Mn6 (example) -
FIG. 4 : Catalytie test results for Mn8 (comparative example) -
FIG. 5 : Activity/stability diagram for the described samples. - Elemental Analysis
- The composition of the calcined catalysts was determined by inductively-coupled plasma optical emission spectroscopy (ICP-OES). 50 mg of catalyst was dissolved in 50 ml of 1 molar phosphoric acid (VWR, analytical grade) at 60° C. To dissolve the manganese dioxide that forms, 50 mg of Na2SO3 (Sigma-Aldrich, analytical grade) was added to the solution. The solutions were cooled and then diluted 1/10 and filtered through 0.1 μm filters (Pall). The calibration solutions were made up at concentrations of 1, 10, and 50 mg l−1 (Merck). The metal concentrations were determined using an Agilent 700 ICP-OES.
- Determination of Specific Surface Area
- The specific surface areas of the catalysts (SBET) were determined by N2-BET analysis on a Nova 4000e (Quantachrome). For this, 100 mg of catalyst was degassed for 3 hours at 120° C. and adsorption and desorption isotherms were then recorded in the 0.007 to 1 p/p0 range. The BET surface area was determined using the data points in the 0.007 to 0.28 p/p0 range.
- Chemisorption
- Chemisorption experiments were carried out on an Autosorb 1C (Quantachrome). Before measurement, 100 mg of catalyst was activated at 500° C. in 10% H2 in N2 for 6 hours. The heating ramp was 2 K min−1.
- The metal surface area (SMET) was determined in accordance with DIN 66136-2 (vers. 2007-01) by H2 chemisorption at 35° C. For this purpose, 20 adsorption points were recorded equidistantly from 40 mmHg to 800 mmHg. The equilibration time was 2 min for adsorption and 10 min for thermal equilibration. For the determination of the metal surface area, the metal atom/H stoichiometry was set at 1. For the CO2 chemisorption measurements to determine the CO2 uptake capacity (U(CO2)), the equilibration time for adsorption was set at 10 min with the parameters otherwise unchanged. Before recording the chemisorption data, any kinetic inhibition of CO2 chemisorption under these conditions was ruled out experimentally. Metal surface areas and CO2 uptake capacities were extrapolated to a pressure of 0 mmHg by the extrapolation method.
- Synthesis
- The catalysts were prepared by co-precipitation, with the nickel/aluminum atomic ratio set at 1. To investigate the effect of iron on the behavior of the catalyst, iron(III) nitrate was added to the nickel nitrate/aluminum nitrate salt solution during the synthesis of the catalyst. To investigate the concomitant effect of iron and manganese on the behavior of the catalyst, manganese(II) nitrate and iron(III) nitrate were added to the nickel nitrate/aluminum nitrate salt solution during the synthesis of the catalyst. All chemicals used were of analytical grade purity. Water was purified in a Millipore filter system and the purity verified by conductivity measurements. The synthesis was carried out in a double-jacketed stirred-tank reactor with a capacity of 3 I. The thermostat fitted to the water-filled double jacket allowed the temperature to be maintained at 30° C. during the synthesis run and two baffles were employed for better mixing. Stirring was carried out using a precision glass stirrer operating at 150 rpm. For the synthesis, the stirred-tank reactor was charged with 1 I of H2O, which was adjusted to pH 9±0.1. The addition of the mixture of dissolved nitrates was carried out at a rate of 2.5 ml min−1. The controlled addition of the precipitation reagent at the same time served to maintain the pH. The starting materials used were one-molar solutions of the respective nitrates (Ni(NO3)2.6H2O, Al(NO3)2.9H2O, Fe(NO3)3.9H2O, and Mn(NO3)2.4H2O). These were mixed, as shown in Table 2, to a total volume of 120 ml min−1 before undergoing dropwise addition to the reactor. The precipitation reagent used was a mixture of equal volumes of 0.5 M NaOH and 0.5 M Na2CO3 solutions, which was added using a titrator. The suspension was aged overnight in the mother liquor with constant stirring, after which the precipitate was filtered off and washed with H2O until the filtrate was of neutral pH. After drying overnight at 80° C. in a drying cabinet, the dried precipitate (precursor) was heated to 450° C. at a heating rate of 5 K min−1 and calcined for 6 hours in synthetic air.
- Activity and Stability Measurement
- In order to be able to compare different catalysts in terms of their CO2 methanation activity, a test program was developed that information on their activity and stability. For this, 25 mg of catalyst from the 150-200 μm sieve fraction was diluted with nine times the amount of SiC and placed in the reactor. The successive measurement steps performed—reduction, equilibration, S-curve 1, ageing, S-curve 2—are shown in detail in Table 1.
-
TABLE 1 Parameters for the measurement steps for determination of the activity and stability profile Reaction gas, Dura- ratio Reaction gas Q pabs tion H2/CO2/Ar [l (STP) gcat −1 h−1] T [° C.] [bar] [h] Reduction 5/0/95 130 485 1 8 Equilibration 4/1/5 150 260 7 24 S-curve 1 4/1/5 150 170-500 8 — Ageing 4/1/5 150 500 7 32 S-curve 2 4/1/5 150 170-500 8 — - To determine the temperature-CO2 conversion curves, the temperature was increased in 25° C. increments in the specified range and the activity in each case determined. A comparison of the two S-curves before and after ageing for 32 hours at 500° C. gives an insight into the stability of the systems to high temperatures.
- As a measure of the activity, on a representative basis, the temperature T75.1 necessary to achieve a CO2 conversion of 75% during the S-curve 1 measurement step was determined. For this, the temperature was increased in 25° C. increments in the specified range. The lower T75.1 is, the higher therefore the activity of the catalyst.
- As a measure of the activity after ageing, on a representative basis, the temperature T75.2 necessary to achieve a CO2 conversion of 75% during the S-curve 2 measurement step was determined. For this, the temperature was increased in 25° C. increments in the specified range. The lower T75.2 is, the higher therefore the activity of the catalyst after ageing.
- Calculation of the difference between T75.1 and T75.2 from the two conversion temperature characteristics gives a measure of the stability of the catalyst. Here too, the smaller the difference, the more stable the catalyst. For better comparability, all calculated activities and stabilities were normalized with reference to the nickel-aluminum oxide catalyst without promoter (Ni). The normalized activity and stability are given by the following expressions:
-
- The results in
FIGS. 1 to 4 show that addition of a manganese promoter to a Ni/AlOx catalyst results in a significant increase in catalyst activity. -
-
TABLE 2 Molar metal salt solutions used in the co-precipitation Example VNi(NO3)2 VAl(NO3)2 VFe(NO3)3 VMn(NO3)2 No. Catalyst [ml] [ml] [ml] [ml] Comparative examples 1 Ni 60.0 60.0 2 Fe2 59.0 59.0 2.0 3 Fe4 57.0 57.0 6.0 4 Fe7 55.0 55.0 10.0 5 Fe10 52.5 52.5 15.0 6 Mn1 59 59 — 2 7 Mn4 57 57 — 6 8 Mn11 51 51 — 18 9 Fe4Mn4 54.29 54.29 5.71 5.71 10 Fe4Mn1 56.10 56.10 5.90 1.90 11 Fe5Mn4 53.38 53.38 7.63 5.62 12 Fe5Mn1 55.13 55.13 7.88 1.87 13 Fe6Mn4 52.47 52.47 9.54 5.52 14 Fe7Mn1 54.16 54.16 9.85 1.84 Examples 1 Mn6 55 55 — 10 2 Mn8 52.5 52.5 — 15 3 Fe3Mn6 52.47 52.47 5.52 9.54 4 Fe5Mn6 51.62 51.62 7.37 9.39 5 Fe6Mn6 50.77 50.77 9.23 9.23 -
TABLE 3 Composition of the calcined catalysts Element contents [%] [% by wt.] Atomic ratios Example Catalyst Ni Mn Fe Al Ni/Al Ni/Mn Ni/Fe Comparative examples 1 Ni 44.3 — — 19.8 1.03 — — 2 Fe2 40.0 — 1.7 19.4 0.95 — 22.0 3 Fe4 39.7 — 4.3 19.4 0.94 — 8.8 4 Fe7 39.6 — 6.9 17.3 1.05 — 5.4 5 Fe10 36.1 — 10.1 17.9 0.93 — 3.4 6 Mn1 38.7 1.3 — 18.0 0.99 27.3 — 7 Mn4 38.9 3.7 — 18.2 0.98 9.8 — 8 Mn11 34.0 10.8 16.2 0.97 3.0 — 9 Fe4Mn4 39.9 17.8 4.2 4.0 1.03 9.0 9.5 10 Fe4Mn1 39.5 17.7 1.3 3.9 1.03 28.9 9.7 11 Fe5Mn4 38.1 17.3 3.8 5.3 1.01 9.4 6.8 12 Fe5Mn1 38.7 17.4 1.2 5.3 1.02 29.4 6.9 13 Fe6Mn4 36.9 18.2 3.5 6.2 0.93 9.8 5.6 14 Fe7Mn1 37.2 16.0 1.3 6.5 1.07 26.5 5.4 Examples 1 Mn6 36.3 6.1 — 15.5 1.08 5.6 — 2 Mn8 31.9 8.3 — 15.2 0.97 3.6 — 3 Fe3Mn6 35.6 16.0 6.0 3.4 1.02 6.0 10.0 4 Fe5Mn6 36.3 16.6 6.1 4.8 1.01 5.5 7.2 5 Fe6Mn6 34.1 16.8 5.8 5.9 0.93 5.5 5.5 -
TABLE 4 Characterization data for the catalysts SBET a Smet a U(CO2)a Example Catalyst [m2 gcat −1] [m2 gcat −1] [μmol gcat −1] Comparative examples 1 Ni 209 21.1 172 2 Fe2 227 19.8 199 3 Fe4 244 18.3 198 4 Fe7 216 11.4 196 5 Fe10 250 9.3 188 6 Mn1 211 19.2 197 7 Mn4 223 20.1 215 8 Mn11 213 10.8 242 9 Fe4Mn4 275 12.9 345 10 Fe4Mn1 241 16.1 204 11 Fe5Mn4 238 17.8 298 12 Fe5Mn1 251 17.6 269 13 Fe6Mn4 262 7.6 276 14 Fe7Mn1 237 11.2 223 Examples 1 Mn6 231 20.0 244 2 Mn8 214 17.6 240 3 Fe3Mn6 249 11.9 277 4 Fe5Mn6 268 15.8 327 5 Fe6Mn6 239 5.5 322 *normalized to mass of the calcined catalyst -
TABLE 5 Results for the catalytic test reaction T75.1 T75.2 Normalized Normalized Example Catalyst [° C.] [° C.] T75.2/T75.1 activity stability Comparative examples 1 Ni 289.41 314.11 1.085 1.000 1.000 2 Fe2 279.29 296.86 1.063 1.036 1.021 3 Fe4 275.05 293.37 1.067 1.052 1.018 4 Fe7 276.35 286.84 1.038 1.047 1.046 5 Fe10 290.54 319.21 1.099 0.996 0.998 6 Mn1 282.04 300.91 1.067 1.026 1.017 7 Mn4 274.57 293.36 1.068 1.054 1.016 8 Mn11 269.95 289.67 1.073 1.072 1.011 9 Fe4Mn4 266.34 280.27 1.052 1.087 1.031 10 Fe4Mn1 274.18 286.01 1.043 1.056 1.040 11 Fe5Mn4 264.02 275.09 1.042 1.096 1.042 12 Fe5Mn1 262.62 271.83 1.035 1.102 1.049 13 Fe6Mn4 270.01 278.48 1.031 1.072 1.052 14 Fe7Mn1 269.11 280.15 1.041 1.075 1.043 Examples 1 Mn6 256.71 275.50 1.073 1.127 1.011 2 Mn8 259.31 272.67 1.052 1.116 1.032 3 Fe3Mn6 253.42 278.06 1.097 1.142 0.989 4 Fe5Mn6 258.16 281.24 1.089 1.121 0.996 5 Fe6Mn6 266.56 290.13 1.088 1.086 0.997
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CN111495374A (en) * | 2020-05-13 | 2020-08-07 | 黄冈师范学院 | Coated CoNi/Al2O3Catalyst, preparation method and application thereof |
US11261137B2 (en) * | 2018-03-09 | 2022-03-01 | Clariant International Ltd | Manganese-doped nickel methanization catalysts having elevated sulphur resistance |
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CN115672331A (en) * | 2021-07-23 | 2023-02-03 | 国家能源投资集团有限责任公司 | Methanation catalyst and preparation method and application thereof |
CN116060049B (en) * | 2021-10-29 | 2024-05-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method and application thereof |
CN114917921A (en) * | 2022-06-08 | 2022-08-19 | 珠海格力电器股份有限公司 | NiMnAl hydrotalcite-like catalyst and preparation method and application thereof |
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